CLASSIFICATION OF CHEMICAL REACTIONS AND REAGENTS

The classification of chemical reactions based on a conception of their mechanism

is most widely used in organic chemistry.
The way of bond cleavage, the nature of intermediates, the electronic nature of an
attacking reagent and other factors are considered.

According to the way of bond cleavage (breaking the bond) reactions are
divided into following types:
- homolytic (symmetric breaking down of a two-electron covalent bond with the
formation of two free radicals A·¦·B→ A· + B·),
- heterolytic (the asymmetrical breaking down of the bond, resulting the
occurrence of two particles with opposite charges A:¦B → Aˉ + B+);
- pericyclic or molecular (synchronous breaking down of old and formation of
new chemical bonds).

According to the nature of intermediates reactions are divided into radical, ionic
etc.
- Radical reactions proceed with the participation of free radicals.
Free radicals are not charged particles containing an unpaired electron (one-
electron atomic orbital):

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 - Ionic reactions are carried out with the assistance of the charged particles
(carbocations or carbanions).
Carbocations are organic cations containing positively charged carbon atom:

Carbanions are organic anions containing negatively charged carbon atom:

- Pericyclic reactions proceed without the formation of intermediate active

particles, in such reactions there is a synchronous breaking down of old and formation of
new chemical bonds:

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 Reactions, proceeding under the ionic mechanism, are subdivided into
nucleophilic (N) and electrophilic (E), depending on the nature of an attacking
reagent.
Nucleophilic reagents are those which give electron pair for chemical bonding
with a substrate. Nucleophilic reagents are:
- neutral molecules containing at least one lone pair of electrons:

- ions bearing the negative charge (anions):

- molecules having centres with raised electron density:

Electrophilic reagents are those which are accepting an electron pair from the
substrate in the formation of a chemical bond with it. Electrophilic reagents are:
- cations: Н+, NO2+, Cl+, etc.;
- neutral molecules having vacant orbital: AlCl3, FeBr3, etc.;
- centres with decreased electroni density:

- halogens: Cl2, Br2, I2 (in the presence of Lewis acids). 3

 The classification of chemical reactions, which is widely used in organic
chemistry by formal signs, is worthy:

1. Addition reactions are designated by a symbol «A».

These reactions are typical for compounds, containing multiple bonds:

Addition reactions can proceed under the following possible mechanisms:

a) electrophilic addition (АЕ);
b) nucleophilic addition (АN);
c) free-radical addition (АR);
d) molecular (synchronous) addition.

2. Substitution reactions are designated by a symbol «S».

They are characteristic for all classes of organic compounds and can proceed
under the following mechanisms:
a) electrophilic substitution (SE);
b) nucleophilic substitution (SN);
c) free-radical substitution (SR).
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 3. Elimination reactions are designated by a symbol «Е».

4. Rearrangements.

5. Oxidation and reduction reactions are accompanied by the changing of

the oxidation state of carbon atom which is the reaction center.

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 ACIDITY AND BASICITY OF ORGANIC COMPOUNDS
For an estimation of acidity and basicity of organic compounds two theories are
applied:
- the Bronsted theory;
- the Lewis theory.

Bronsted acids and bases

According to the Bronsted theory, an acid is a compound that donates a
proton, and a base is a compound that accepts a proton.
Thus, the acid is a proton donor, and the base is a proton acceptor:

Types of organic acids

Depending on the nature of an element which is bonded with hydrogen atom,
acids are divided into four principal groups:
- OH-acids: carboxylic acids (RCOOH), alcohols (AlkOH), phenols (ArOH), etc.
- SH-acids: thiols (RSH), thiolic acids (RCOSH), etc.
- NH-acids: amines (RNH2), amides (RCONH2), etc.
- CH-acids: hydrocarbons and their derivatives.

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 Types of organic bases
Two types of Bronsted bases are distinguished:
- p-bases or onium (the presence of atoms with lone pair of electrons);
- π-bases (the presence of -bond).

Depending on the basicity center the onium bases are divided into three
principal groups:
- Ammonium bases: primary (RNH2), secondary (R2NH) and tertiary
(R3N) amines; azometines (RCH=NR); nitriles (RCN); nitrogen containing heterocycles;
- Oxonium bases: alcohols (ROH); ethers (ROR); aldehydes (RCOH);
ketones (RCOR’); functional derivatives of carboxylic acids (esters (RCOOR’), acyl
halides (RCOHal), amides (RCONH2), etc.);
- Sulphonium bases: thiols (RSH); thioethers (RSR).

LEWIS ACIDS AND BASES

The Lewis theory of acids and bases, unlike the Bronsted theory, is more
general.
By Lewis, the base is the donor, and the acid - an acceptor of the electron 7pair.